Process of extracting manganese from ore



INVENTORS jini/waff' Sweef BY n rfaZfr /Yacvfar MMM/mr,

A. T. SWEET ET AL PROCESS oF EXTRACTING MANGANESE FROM ORE original Filed April 29,-1929 June'l2,1934.

Patented-June l2, 1934 I V 1,962,169 PROCESS or Ex'rnAo'rlNG MANGANESE FROM oRE Andrew T. Sweet, Houghton, and John D. Mac- Carthy, Detroit, Mich., assignors to General Manganese Corporation, Detroit, Mich., a corporation of Delaware Application April 29, 1929, serial No. 359,155

Renewed August 18, 1933 25 Claims. (Cl. 75-18) The invention relates to an-improved process The main feature of our invention resides in for separating manganese from its ore, particuthose steps of the process wherein the manganese larly the low grade ores wherein the manganese is extracted from the ore and separated from. is associated with relatively large amounts of most of the other materials in the ore by a differ- 6 other materials. ential leaching process. Our invention cvonteme@ Among the objects of the invention are the folplates the processing of the crushed ore material lowing: through a counter current decantation utilizing First, to devise an economical process that can a solublel chloride leach. The ore is fed to the be applied to available manganese deposits and iirst leaching tank of a series, the number of lo obtain therefrom at a reasonable cost a mangatanks of which depends on the richness of the g nese product in a commercial form. ore and the amount of manganese in the tailing Second, to provide a process for obtaining relaof the series. The solid material settling to the tively pure manganese oxide free from those imbottom of the rst tank iS delivered to the secpurities which are detrimental 'in metallurgical ond tank and that from the second tank is delivl processes utilizing the manganese product. ered to the third tank and so on until the tailing 70 Third, to provide a process for beneciating from the last tank is practically free from mancertain manganese bearing materials which ganese. Water is introduced into the last tank heretofore have not been amenable to known and the overflow processed successively to the methods of treatment. other tanks of the Series and iS withdrawn from 2o Fourth, to obtain manganese from complex the rst tank. The soluble chloride, which pref 75 carbonate ores, mangano-siderites and the like. erably is a solution of chlorine gas or hydro- Fifth, to obtain an eicient method for the sepchloric acid, is introduced into one of the interaration of manganese from iron in an economical v'mediate tanks of the series. The object of the manner. process is to render the manganese in a soluble Sixth, to obtain manganese from its ores in a form and to effect a separation of the manganese su, form practically free from phosphorus; from the iron and the less Soluble impurities in Seventh, to obtain a chemical process for the the ore. Since the iron compounds in the ore are separation of manganese from the' other matenormally'soluble in hydrochloric acid the Success rials associated in the ore. of our process depends upon maintaining the 3o Eighth, to obtain a chemical process resulting proper concentrations so as to preferentially disw in by-produ'cts of commercial value. solve the manganese and leave the iron substan- ,While in the broader aspects our invention tially undissolved. We have discovered that a dealsV with the separation of manganese from differential leach can be carried out with anore other materials such as iron which are ordinarily of the above mentioned analysis by maintaining associated with the manganese in the mangathe concentration of the hydrochloric acid in the 90 nese bearing materials, our invention is particurst tank of the series not in excess of 1%. The larly applicable to the extraction of manganese introduction of raw ore at this point causes a from low grade ores such as the complex carprecipitation of anyv soluble iron compounds. bonate ores, mangano-siderites, etc., and in the ln some instances it may be desirable to per- 40 following detailed description reference will be mit a. certain percentage lof iron to be extracted 95 made to an ore which after being separated from with the manganese and the amount of iron in t While our process is not necessarily carried The accompanying drawing discloses a flow out in any particular type of apparatus, that sheet for one process of extracting an ore ofthe which seems to be best Suited from a'commerabove analysis. cial lstandpoint is a series of Dorr tanks or thickno eners. Since this apparatus is well known in various ore extracting industries, a detailed description of the same will not be entered into in this application.

With the ore of the above analysis the solution withdrawn from the No. 1 thickener, illustrated in the flow sheet, contains chiefly manganese and calcium chloride solutions. This solution after passing through a clarifier may be further treated to obtain a separation of the manganese in various different Ways. 'I'he manganese may be separated electrolytically by utilizing a carbon electrode multiple cell electrolytic apparatus. This treatment is indicated diagrammatically on the ow sheet by the dotted line.

Another method of separating the manganese depends upon a chemical separation and is illustrated in full lines on the flow sheet. The manganese chloride and calcium chloride solution is passed to a precipitation tank in which magnesium oxide is introduced. The manganese is thus precipitated and may be filtered from the solution as manganese hydroxide which when roasted in a furnace results in a high grade manganese sintery approximating MnaOl. The ltrate from the precipitation tank contains magnesium chloride and calcium chloride and to preserve these products they are passed to a carbonating tank where an excess of magnesium oxide is added, together with carbon dioxide gas. This forms calcium carbonate which may be calcined to produce lime and the carbon dioxide gas collected and fed back into the carbonating tank. .The magnesium chloride in the filtrate may be subjected to distillation, thereby obtaining magnesia and free chlorine gas. The magncsia is then available for the precipitation step of the process, while the chlorine is available for introduction into the counter current decantation process. Thus with the arrangement specified the process may be carried out with very little cost for chemical reagents since the byproducts of the process can be utilized in this capacity.

While the process as above described has indicated that a soluble chloride was the preferred solvent for the preferential extraction of the manganese, our invention is not to be construed as limited to this solvent as there are other reagents Which can be used in carrying out our separation. For example, it is possible to extract manganese by a sulphuric acid leach providing the concentrations are maintained in the proper relationship. It should be noted that where an excess of sulphuric acid is used soluble compounds will be formed with the iron, manganese and magnesium in the ore, whereas an insoluble compound is formed with the calcium. We have disccvered, however, that the manganese may be separated from the iron by maintaining a sufficient proportion of the ore in the No. 1 thickener, this resulting in a preferential solution of the manganese sulphate over the iron sulphate.

In the broader aspects of our invention it includes the use of soluble chlorides and soluble sulphates as leaching materials and also other similar solvents which normally would dissolve manganese and also other impurities in the ore but which under proper control of concentration will cause a separation of the manganese from one or more of the less readily soluble metallic impurities.

What we claim as our invention is:

1. The process of extracting manganese which' consists in treating manganese carbonate ore with a solvent for manganese and maintaining the concentration of the solvent below a predetermined amount at the point of separation of the solvent and solid, thereby controlling the amount of material other than manganese dissolved in the solvent.

2. The process of extracting manganese which consists in treating manganese carbonate ore with a soluble chloride and maintaining the concentration of the soluble chloride below a predetermined amount at the point of separation of the liquid from the solid material, thereby controlling the amount of chloride soluble material other than manganese dissolved in the liquid.

3. The process of extracting manganese which consists in treating manganese carbonate ore with hydrochloric acidl and maintaining the concentration of the hydrochloric acid below a predetermined amount at the point of separation of the solution and the solid matter, thereby controlling the amount of chlorides other than manganese contained in the solution.

4. The process of extracting manganese from manganese carbonate ore containing iron which consists in treating the material with a soluble chloride and maintaining the concentration of the chloride below a predetermined amount at the point of separation of the solution and the solid mattei, thereby controlling the amount of iron chloride in the solution.

5. The process of extracting manganese which consists in treating the manganese bearing ore with a solvent for both manganese and an impurity in the ore, separating the manganese from the impurity by providing relative concentrations of ore and solvent such as to maintain the manganese in solution and maintain said impurity out of solution and separating the solution from the solid matter.

6. The process of extracting manganese which consists in treating manganese carbonate ore with a soluble chloride and in separating manganese from another metal associated therewith by maintaining the concentration of the ore and the soluble chloride such as to preferentially dissolve manganese leaving the aforesaid other metal undissolved and separating the manganese solution from the solid matter.

7. 'I'he process of extracting manganese which consists in treating manganese carbonate ore with a hydrochloric acid leach and maintaining the concentration of the ore and acid such as to preferentially dissolve manganese leaving another metallic impurity undissolved.

8. The process of extracting manganese which consists in subjecting manganese bearing ore to counter current decantation,.utilizing a soluble chloride leach and in maintaining the proportion of chloride to ore at the out-flow of the leaching solution such as to dissolve the manganese preferentially over another metallic compound.

9. The process of extracting manganese which consists in treating manganese carbonate ore with a solvent for both manganese and iron and in separating the manganese from the iron by providing sulicient concentration of said manganese carbonate ore to keep the iron out of solution to any substantial extent while converting the manganese into soluble form and separating the solution from the solid matter.

10. The process of extracting manganese which consists in treating manganese carbonate ore with a soluble chloride and in separating mansufficiently low t prevent substantial solution of i the iron and in maintaining the concentration of -the leach at the out-go of the solid materials such as to extract substantially all of the manganese from the manganese carbonate ore.

13. 'I'he process of extracting manganese which consists in treating manganese carbonate ore to a hydrochloric acid leach and maintaining the concentration of the acid'less than 1% at the point where the leach is Withdrawn from the ore.

A14.. 'I'he process of extracting manganese from a carbonate ore containing the same consisting in first separating the manganese from the iron by a chloride leach in a counter current decantation apparatus and in subsequently separating the manganese from other soluble compounds contained in the leach.

' 15. The process of extracting manganese from a carbonate -ore containing thesame which conconsists in subjecting manganese carbonate ore containing manganesairon, lime and silica to countercurrent decantation, utilizing as a leach a solvent, for both manganese and iron and maintaining the concentration of said solvent at the out-now of the leach sufficiently low by adding ore thereto whereby solution of the iron is substantially prevented.

17. The process of extracting manganese which consists in subjecting manganese carbonate ore containing manganese, iron, lime and silica to countercurrent decantation. utilizing as a leach a soluble chloride and maintaining the concentration oi said chloride at the out-flow oi.' the leach suiliciently low by adding ore thereto whereby solution of the iron is substantially prevented.

18. The process of extracting manganese which consists in treating manganese carbonate ore with an inorganicsoluble material containing anV acid' radical and maintaining the concentration of said soluble material below a predetermined amount at the point of separation of the liquid from the solidmaterial, thereby controlling the amount of material other than manganese dissolved in the liquid.

.another metal associated therewith by maintain- 19. 'I'he process of extracting manganese which consists in treating manganese carbonate ore with an inorganic soluble material containing an acid radical and in separating manganese from amount of reagent-soluble material other than manganese dissolved in the liquid.

21. The process of extracting manganese comprising treating the manganese-bearing material with a reagent of the class comprising strong inorganic acids and the soluble salts thereof having a preferential soluble action on manganese and maintaining the concentration of the soluble reagent below a predetermined amount at the point of separation of the liquid from the solid material, thereby controlling the amount of reagent-soluble material other than manganese dissolved in the liquid.

22. The process of extracting manganese comprising treating manganese-bearing material with a reagent of the class comprising soluble chlorides and sulphates and in separating manganese from iron by maintaining a suiiicient concentration of manganese-bearing material to maintain the iron substantially insoluble and the manganese soluble.

23. The process of extracting manganese from= carbonate ores containingl manganese, iron and an alkaline earth metal compound comprising digesting said manganese ore with a reagent of the class comprising soluble chlorides and soluble sulphates and separating manganese from iron by maintaining a suiilcient concentration of said ore to maintain the iron substantially insoluble and the manganese soluble. f

24. 'I'he process of extracting manganese from carbonate ores containing manganese, iron and an alkaline earth metal compound comprising digesting said manganese ore with a soluble ,chloride and separating manganese' from iron by maintaining a sumcient concentration of said ore to maintain the iron substantially insoluble and the manganese soluble.

25. The process of obtaining a soluble manganese compound from a carbonate ore containing manganese, iron and alkaline earth metal compounds comprising'digesting saidcarbonate ore with a' reagent of the class comprising soluble 135 chlorides and soluble sulphates and maintaining a sumcient concentration of said ore tomaintain thev iron in the form of an insoluble iron com- 

